Treatment of polyamide fibrous material with titanium trichloride

ABSTRACT

A method for processing polyamide fibrous material, especially nylon products, wherein the fibrous material is treated with a solution or dispersion including TiCl3 and polyethylene, thereby providing the material with full-dullness and non-waxy touch.

United States Patent Matsuda et al.

1451 Apr. 4, 1972 TREATMENT OF POLYAMIDE FIBROUS MATERIAL WITH TITANIUM TRICHLORIDE Inventors: Shogo Matsuda, Toyonaka-shi, Osaka; Yu-

taka Shimodoi, Suita-shi, Osaka; Takeo Oshima, Ibaragi-shi, Osaka; Kazushi Ochi, Neyagawa-shi, Osaka, all of Japan Assignee: Asahi Kasei Kogyo Kabushiki Kaisha,

Osaka, Japan Filed: Dec. 12, 1967 Appl, No.: 689,314

Foreign Application Priority Data Dec. 15, 1966 Japan ..41/82307 us. c1 ..8/130.1,8/115.6, 8/115.7, 8/DIG. 21, 8/DIG. 4, 8/DIG. 10, 8/DIG. 1, 8/175, 8/17,117/138.8 N, 117/118, 117/161ZA,

161.01 1.1106111 3/30, D06m 3/40 Field 61 Search ..8/130.1, 115.5, 115.7,15105 911,282 1l/1962 Great Britain Primary Examiner-Donald Levy Assistant Examiner-B. Bettis Att0rneySughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A method for processing polyamide fibrous material, especially nylon products, wherein the fibrous material is treated with a solution or dispersion including TiCl and polyethylene, thereby providing the material with full-dullness and nonwaxy touch.

22 Claims, No Drawings TREATMENT OF POLYAMIDE FIBROUS MATERIAL WITH TITANIUM TRICHLORIDE BACKGROUND OF THE INVENTION This invention relates to a novel process for finish-treatment of polyamide fibrous materials including fibers, filaments, tows, yarns, threads, knitted-, woven and non-woven fabrics, for providing them with superior full-dullness and handlings, without sacrificing any appreciable loss of the strength of the products.

Polyamide fibers are highly superior in their strength and dyeing characteristics, and therefore find their vast and broad availability in the fields of industrial application; domestic appliances and especially clothing products. Various and profound investigations have been made toward providing, in addition to said superior and desirous characteristics, other various characteristics which are peculiar to common natural fibers such as wool, cotton and the like, to polyamide fibers which are defective on account of its remarkable transparent and waxy appearance and lack ot moisture-absorbing characteristic. When polyamide fibers are utilized for fabrics for clothing, inferior appearance, touch, handling and wearing contact are necessarily encountered.

Hitherto therefore, considerable conditioning efforts have been directed by those skilled in the art to obviate the transparency and glass-like feel as well as waxy touch from polyamide fibers, thus providing generally full-dullness thereto.

According to one representative aspect, the surface conditions of polyamide fibers are modified by being subjected to the action of certain reagents such as hydrochloric acid, sulfuric acid, zinc chloride or the like. By adopting this kind of surface conditioning measure, the transparent and waxy appearance and touch of polyamide fibers can substantially be obviated, but, on the other hand, the stiffness of the fibers is highly accentuated and thus fabrics made up of these conditioned fibers provide a paper-like feel to the wearer. In addition, a considerable reduction of the strength of the fibers inevitably takes place. This newly invited defect has considerably prevented these surface-conditioned polyamide fibers from being practically utilized on a large'scale in the textile industry. The technical reason for the accentuated stiffness in the surface-conditioned polyamide fibers in the above sense can be attributed to the fact that at least a part of the polyamide fibers is dissolved by contact with the conditioning reagent, such as hydrochloric acid, causing strong sticking take place among the fibers and further even among the threads fabricated therefrom.

SUMMARY OF THE INVENTION The main object of the invention is therefore to, provide a unique process for providing full-dullness to and obviating transparent feelings from, polyamide fibrous material without deleteriously sacrificing the strength thereof.

A further and secondary object is to provide a fiber-conditioning process of the above kind, capable of providing polyamide fibrous material having a non-waxy and soft touch.

For the realization of the above objects, it is proposed according to the present invention in its characterizing and broad sense that polyamide fibrous material be brought into contact with TiCl as an agent adapted for swelling polyamide fibers, and a separating agent, adapted for separating swollen polyamide fibers from each other.

DETAILED DESCRIPTION OF THE INVENTION By the term polyamide used herein and throughout this specification is meant any long-chain polymeric or copolymeric amide which has recurring amide groups as an integral part of the main polymer or copolymer chain, and which is capable of being formed into a filament in which the structural elements are oriented in the direction of the axis. Among others are included nylon 6 and nylon 6, 6. Such other linear polymers as nylon 1; nylon 2; nylon 3; nylon 4; nylon 5; nylon polyrhethoxylene adipamide or f g a:

HN-HzC-fA-CHrNH-C-CI-Iz-CH -CH -CII l s J.

poly-m-phenylene isophthalamide or polyhexamethylene terephthalamidc or several examples of the latter may preferably be:

Q-met-hyl-IO nylon or Although the invention is mainly directed to synthetic fibers of polyamide and fibrous products thereof, it is also applicable to a mixture of synthetic polyamide fibers with other kinds of fibers, for instance, natural fibers such as wool, cotton, silk and the like, and/or regenerated fibers such as viscose rayon, cupra rayon, polynosic acetate or the like fibers, and/or other artificial fibers such as those of polyacrylonitrile, polyester, polyvinylchloride, polyvinylidenechloride and the like, so far as polyamide fibers are substantially contained. Mixed yarns and mixed fabrics may also be treated according to the process of the present invention, as far as they are substantially composed of polyamide fibers or of mixed fibers in the above sense, as a whole. Non-woven fabrics may be equally treated according to the novel technique as proposed by the present invention. Therefore, for accurate and precise understanding of the present invention, the term polyamide fibers or polyamide fibrous material must be interpreted as covering those which have been enumerated above. Dyed and non-dyed materials of the above kind may equally be treated by the process as proposed. White or colored prints may also be realized as will be more fully described hereinafter.

TiCl: as the main swelling agent may be used in combination with an auxiliary or secondary swelling agent or agents.

As the auxiliary swelling agent employable in this invention, one or more carboxylic acids may be used, such as:

formic acid (65-80%); monochloroacetic acid (45-90%);

monochloropropionic acid (10-80%); malonic acid (65-95%); arcylic acid (l595%); glyoxal acid l 0-70%);

Mineral acids such as HCl (10-35%); HBr (5-45%); HNO (15-60%); H 50 (20-98%); 0- and p-phosphoric acid (15-95%); H PHO (20-90%); HPH O (10-90%) or the like may also be employed for such additional swelling agents. Amides, such as dimethylformamide, are also employable.

In place of the aforementioned various acids and amides and combinations thereof, various acid halides made be used such as:

acethylbromide (4580%); acethylchloride (30-80%).

Sulfonic acids or its derivative such as:

benzenesulfonic acid (IO-90%);

toluensulfonic acid (2-95%); and/or phenols or its derivatives such as:

nitrophenol (5-95%); chlorophenol (lo-100%); cresol (5-l00%); p-nitrophenol (5-95%) and the like may be used.

Sulfoxide such as dimethyl sulfoxides, or the like, may equally be used.

Metal halides, such as:

LiCl (45-70%); MgCl, (15-80%); AlCl, (35-65%);

CuCl, (SO-65%); ZnCl, l-85%); FeCl, (lo-50%);

l-eCl (20-85%); MnCl (40-60%); CoCl (40-50%);

TiCl (20-80%);TiCl (IO-100%); SnCl, (30-75%);

SnCl (15-90%); SnCl (5-l00%); SbCl (20-85%);

CuCl, (SO-65%); SiCl (5-l00%); FCl (5-l00%);

POCl, (20-80%); ZnTiCl 10-70%); Zn( 13H) (35-70%);

LiBr (60-80%); NaBr (60-65%); AlBr, (30-65%);

CaBr, (15-70%); ZnBr, (IO-85%); CoBr, (30-60%);

NiBr, (40-60%); SnBr (30-65%); CuBr, (4070%);

SiBr (IO-100%); Lil (75-90%); NaI (55-80%); KI

(40-80%); All (30-70%); Cal, (-65%); Znl l0-85%); Col

(50-80%) and the like may also be used.

Sulfates such as:

FeSO, (40-70%); MnSO, (20-95%) and the like may also be used.

Any one of the salts above enumerated may be used in the form of solution, dispersion or emulsion in an organic solvent or water. In the above description, percentages parenthesized are meant to be preferable concentrations and are not meant to be limiting in any manner.

The separator or the agent adapted for preventing swollen fibers from sticking together may be enlisted'in the following manner. These agents may be used individually or in combination, and preferably in an amount of from about 2-45 percent.

For such separating agents as disclosed herein, any one or a combination of the following substances may be used.

polyolefins, such as polyethylene; liquid paraffin; solid paraffin; and the like;

polyflurocarbons, such as polyperfluoalkylacrylate;

silicon resins, such as dimethyl polysiloxane; methylhydrogen polysiloxane; or the like;

higher fatty acids such as palmitic acid; oleic acid; stearic acid; or the like;

higher monohydric and polyhydric alcohols;

polyoxyethylene or its derivatives such as P.O.E. -alkylphenyl ether; P.O.E. -alkyl ether; P.O.E. -alkyl ester; P.O.E. -alkyl amide and the like;

higher fatty acid derivatives such as alkyl sulfonate;

sorbitan alkyl ester or the like;

higher alkyl quart, ammonium salt such as alkyl dimethyl ammonium chloride or the like; Y alkylbenzenesulfonate; alkylnaphthalenesulfonate or the like;

derivatives of higher alcohol such as -sulfate; -dialkyl sulfosuccinate; -alkylphosphate and the like.

Generally speaking, TiCl as the main swelling agent is used in combination with other or auxiliary swelling agents, preferably in the presence of a solvent such as water or organic solvent, as was referred to hereinbefore.

Or, in the alternative, a reaction mixture used for the preparation of TiCl, starting from TiCL may be used.

A conventional process in this sense was already reported in German magazine Zeitschrift fuer anorganische Chemie, 247, p. 367-387 (1941). In this conventional method, titanium tetrachloride is reacted preferably in the presence of an acid with one or more metals, such as Zn, Fe, Al, Mg, Ca and Ba. Better results may be obtained when the reaction is carried out in the presence of one or more halides of said metals. The acid usable in the above process may be hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid or sulfuric acid. The resultant reaction mixture contains generally titanium trichloride and metal salt or salts, and metal complex salts as may be expressed by .MTiX,, wherein:

M stands for any one of Zn, Fe, A1, Mg, Ca and Ba; and X stands for any one of Cl,, Br,, 1,, F, and S0,.

In the above reaction mixture, the content of TiCl, may

generally amount to l-l8 percent when it is desired for the process of the present invention. To this reaction mixture, other auxiliary swelling agent or agents may be added in the ratio of 2-35 percent.

As will be. readily understood, the improvement by the present invention may be carried out either wholly or partially on the material being treated.

The processing may be carried into effect in a single stage, or alternatively in two successive stages. In the former case, the processing efficiency is naturally higher. In the latter case, the reagent solution or dispersion may be more stable for extended processing times.

More specifically, the process according to this invention may be carried into effect in the following way:

In the case of the single processing stage method, the polyamide fibrous material is treatedwith a mixture of the main swelling agent and the separating agent, preferably in the presence of auxiliary swelling agents. Upon being dipped in the treating bath, the fibrous material is squeezed or centrifuged so as to distribute the treating liquor evenly within the material which may be then air-dried at room temperature. In order to accelerate the productive efficiency on an industrial scale, the material should be preferably heated at elevated temperatures such as 50-l60 C. for a short time duration such as 30 seconds 10 minutes.

When the reagents remain in the fibrous material after treatment, the modifying process will naturally go on which must be avoided for the desired purpose. It is therefore preferable to water-clean the treated material to a satisfying degree so as to remove the remaining reagents from the products.

The process according to this invention is carried out in liquid phase. As the solvent serving this purpose, water or any suitable organic solvent may be adopted. From the industrial point of view, however, the use of water is most preferable.

The quantity of the swelling agent or agents used is selected to be such as to dissolve part of the fibrous material being treated. It is preferable to use at least 5 percent. The quantity of the separating agent used may preferably amount to 2 45 percent.

In addition to the swelling agent and the separating agent, the treating liquor may include any conventional softner, hardener, water-repellant, oil-repellant, anti-static agent, moisture-absorbant, finishing agent, color pigment, dye stuff and the like auxiliary agent or agents.

In the two-stage mode, the fibrous material is treated at first with a solution or dispersion of the separating agent, and then with the swelling agent. The treated material at the first stage is squeezed or centrifuged so as to evenly distribute the separating agent throughout the material. After this treatment, the fibrous material is subjected, upon drying or without drying, to the second stage treatment.

The concentration of the separating agent in water or organic solvent, may amount to 2 45 percent, as was referred to. The solution or dispersion may be used within a certain elevated temperature range for maintaining the stability of the treating liquor. Room temperature will do however in most cases.

The second stage may preferably be carried into effect at l0-90 C. for 3 5 minutes.

with use of less effective swelling material or with use of a relatively dilute solution or dispersion of the swelling agent, the fibrous material after being dipped, taken out and squeezed, must preferably be heated at 60-l50 C. for l 5 minutes.

In the two-stage processing, when employed, various auxiliary agents or additives which have been referred to hereinbefore in the description of the single stage processing mode may naturally be employed. These additives may preferably be added to the second stage treating liquor, preferably in the form of a dip-treating bath.

Although the improvements attainable in accordance with the novel teachings of the invention may be performed upon the polyamide fibrous material as a whole, the process may be, when so desired, carried into effect partially. The best mode for this purpose may be performed in the conventional printing mode. In this way, highly durable and brilliant white and color designs may be obtained, the characterizing feature of which resides in full penetration of the printed designs through the material, thus the designs appear very sharp even from the back side of the fibrous material.

According to the present invention, the conventional waxy and transparent touch and appearance may be substantially obviated and the desirous full-dull effect may be provided to the fibrous material under consideration. When relying upon the printing technique, the swelling agent and the separating agent can be mixed into the printing paste. Pigments and/or dye stuffs may also be added thereto.

As a representative, yet non-limiting mode of the present invention to be carried out in combination with the conventional printing technique, the printing paste can be prepared so as to contain any of of the swelling agents in an amount of about 2 45 percent; a separating agent in an amount of about 0.5 percent and starch or the like paste-fonning material in an amount of about 2 25 percent, so far as virgin polyamide fibrous material is concerned. If the fibrous material has previously been treated with separating agent, the paste must preferably contain the swelling agent in an amount of about 2 45 percent and the starch and the like paste-forming material in an amount of about 2 25 percent.

The printing paste may contain naturally various additives already referred to hereinbefore.

The printed polyamide fibrous material is kept for the time being at room temperature, or heated at a certain elevated temperature such as 50-100 C. preferably for l 8 minutes. The printed areas have an excellent full-dullness, proper degree of soft touch and medium stiffness, yet not having any waxy feeling. After several repeated laundries or dry-cleaning operations, the printed design will not be subjected to any appreciable adverse effect.

When the above-modified printing technique is applied to non-dyed material, which is then dyed conventionally, the printed designs may appear to be less colored, yet non-transparent, while the non-printed or substrate areas will represent a thicker color. On the contrary, when the printing technique is applied to an already dyed material, the printed designs will be of resist-colored and appear to be non-transparent.

As will be noted by reference to the following detailed description of the invention, the products according to the present invention represent desirous and superior full-dullness and non-waxy appearance and touch, without any appreciable loss of the strength of the fibrous material and the obtained characteristi cs are highly durable and permanent considerably irregular surface conditions. It is supposed that the superior full-dullness obtained and the disappearance of the conventional waxy appearance are attributable to the diffused reflection caused by the intentional provision of the irregular surface conditions.

When the fibrous material is treated only with the swelling agent, the treated material, after being dried, will show a highly accentuated stiffness. When the material is in the form of a fabric, the latter will show a considerable paper-like touch which prevents the material definitely from being used for the clothing purpose. On the other hand, a considerable reduction in strength may generally be invited. This phenomenon is attributable to the fact that the swollen or partially dissolved fibers resulting from the above-mentioned treatment will stick together to a large extent which fact has been found from elec- $9. .t-9E9 E2E9E Fi In the course of the processing as proposed by the present invention, polyamide fibers are brought into contact with particles of the separating agent specifically adopted in this invention and these particles adhere to the surfaces of the fibers so that the above-mentioned mutual and adverse sticking phenomenon between fibers may be eliminated by the influence of the intermediate presence of said attached particles of the separating agent. It will be noted that the minute parti cles of the agent will effectively prevent the swollen fibers from direct contacting. It is believed that the strength of the fibrous material is maintained in the present invention by the existence of particles of anti-sticking agents between the fibers which effectively act as a kind of lubricant for allowing considerable mutual slippage when subjected to a heavy load.

The foregoing invention can best be understood by reference to several specific examples which are presented only for purposes of illustration and are not intended to be limiting in any way. Percentages are by weight, if not otherwise specified. A m p n A EXAMPLE 1 I I A treating liquor containing titanium trichloride 10 percent, zinc chloride 5 percent, hydrochloric acid 2 percent and Mykon SF (30% polyethylene emulsion) manufactured by Warwick Chemical Co., Rhode Island, U.S.A., was prepared and a nylon 6,6-yarn, 70 d./24 fils., was passed through a bath fof said liquor and squeezed between a pair of pressure rolls with a pressure of 500 g./cm. This yarn was passed through a furnace at l20 C. for 30 seconds. Then, the yarn was washed with water and dried.

The thus treated yarn showed enough full-dullness and nonwaxy, linen like touch for clothing purposes, without loss of any appreciable strength, while a similar yarn treated with a similar liquor in the absence of said polyethylene emulsion represented too high stiffness to-be used for clothing purpose.

In the following Table l, the resulted physical properties of the both treated yarns are shown in a comparative way.

TABLE I Dullness or non- Folding resistance.

transparency 1 mg./d. Strength, g./d.

After five After five After five Before times laundry Before times laundry Before times laundry laundry tests laundry tests laundry tests Non-treated yarn 68 68 1. 2 1. 0 4. 5 4. 4

Yarn processed according to the invention 82 82 1. 6 1. 4 4. 4 4. 3 Yarn processed in the absence of polyethylene emulsion 83 83 4.2 3.7 4.2 4.1

l The dullness or non-transparency was measured in terms of Witness as appearing when the yarn was wound tightly around a black board.

2 Folding resistance as inverse measure of flexibil 5 cm. of the yarn.

3 Tensile strength per denier, g./d.

When polyamide fibrous material is subjected to the action of the swelling agent according to the present invention, part of the material is made swollen or partially dissolved. After being dried and water-washed, the treated materiampre sents ity was measured in terms of the strength, g./d., as encountered when folding EXAMPLE 7 V V A tafieta, 113 warps X 99 wefts, nylon 6, d./24 fils., was dipped in art aqueous dispersion 7 containing titanium trichloride 10 percent and a 30 percent polyethylene emulsion (Mykon SF referred to in Example 1) 20 percent, and squeezed to a 40 percent pickup based upon dry fabric weight, which is applicable throughout all the examples herein disclosed. The fabric was then heated at 80 C. for 3 minutes, washed by water and dried.

The thus treated fabric showed desirous full-dullness and cotton-like feelings, without representing appreciable paperlike touch and without reducing the strength of the fabric.

In a comparative test, a 10 percent aqueous solution of i titanium trichloride was used and the treating conditions were substantially same as above. The thus treated fabric showed similar dullness as above, yet representing a considerable paper-like touch and a substantially reduced strength.

The comparative results are shown in thefollowing Table l or toughness similar to cotton fabrics, without inviting appreciable paper-like touch and without loss of strength. Waxy feelings of the original non-treated fabric were completely obviated and linen-like touch was newly created.

The above favorably conditioned characteristics did not disappear even afier l0 laundry operations.

Although the characteristics of a corresponding similar raw fabric treated only with said solution A represented similar improvements in dullness and hand feelings, it represented too much paper-like touch to be used for wearable clothes.

The physical properties of the above-processed fabric in accordance with the inventive process are enlisted in the following Table III as set forth for comparison.

. EXAMPLE 4 l n to a similar flask as employed in the foregoing Example 2,

TABLE II Transparency 1 softness Strength 3 After five After five After five Before times Before times Before times laundries laundries 4 laundries laundries 4 laundries laundries 4 Non-treated fabric 100 101 1. 06 1.0 32 31 Processed fab. according to inventive process 87 89 0. 81 0. 84 29 28 Processed fab. only with TiCla 86 87 .0. 40 0. 61 23 24 1 Transparency was measured on a Hitachi spectrophotometer, taking that of non-treated fabric as 100. 2 Softness was measured by Clark's method, taking the mean of those of warp and weft.

3 Strength represents tensile one, taking the mean of those of warp and weft. 3 Strength represents tensile one, taking the mean of those of warp and weft.

4 Laundries were carried out each time by use of a domestic laundry machine, of NATIONAL, no agitator vane, water-jet swirling-type, with cleaning water, 40 0.. mixed with 0.5% of soap, for 5 minutes, followed by clean water cleansing at 40 C. for 5 minutes and further by flowing water cleansing for 6 minutes.

Even after lslaunderings, the fabric processed according to the invention represented no appreciable reduction in its fulldullness and soft touch.

EXAMPLE 3 70 g. of concentrated sulfuric acid and 350 c.c. of water were introduced into a three-neck flask, fitted with a thermometer, an agitator and a dropping funnel, and 250' g. of titanium tetrachloride were droppingly and agitatingly added to the solution. Then, 72 g. of metallic zinc powder were gradually added to the mixture, which, while being kept at 40 C. by outside cooling, was reacted for 1 hour, thereby producing a liquid containing 26 percent of titanium trichloride. This trichloride solution will be referred to hereinafter as liquid A."

A treating liquid mixture was prepared so as to contain said liquid A 40 percent, a 30 percent polyethylene emulsion MARPOZOL PO," manufactured by Matsumoto Yushi Seiyaku Co., Ltd., Osaka, Japan) 12 percent and water 58 per- The thus treated fabric represented full-dullnessand superi tive t e s ts.

100 g. of concentrated hydrochloric acid and 500 c.c. of water were introduced and, while the flask being cooled from outside by means of circulating cold water, 345 g. of titanium tetrachloride were added dropwise. Further, 33 g. of metallic aluminum powder were gradually added to the mixture which was then reacted at 20-30 C. for 1 hour. In this way, a solution containing 26 percent of titanium trichloride was obtained. This solution will be referred to as solution B" hereinafter.

Next, a treating liquor was prepared from 31 percent of said liquid B, 15 percent of 30 percent dimethyl polysiloxane emulsion (Norane Silicone SS," manufactured by Warwick Chemical Co., Rhode Island, U.S.A.) and 54 percent of water, and a crepon fabric, 161 warps X 108 wefts, of nylon 6, 50 d. /17fils., was treated with the liquor in the similar way as diseas EEZ PEESBEB PW-W,

The thus treated fabric showed superior full-dullness and cotton-like touch, without appreciableloss of strength, while a similar fabric treated only with said solution 8 represented considerable paper-like touch, even though the desirous dullness and the like were attained.

The following Table IV shows the results of these compara- TAB LE nr Transparency Softness Strength, kg.

After five I After five After five Before times Before times Before times laundries laundries lanndries laundries laundries laundries Non-treated fabric 100 102 1. 0 1.02 31 30 Processed fabric according t inventive process 76 84 81 28 28 Fabric treated only with solution A 73 73 .25 38 18 22 TAB LE 1V Transparency Softness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries Non-treated fabric 100 101 1. 52 1. 10 32 31 Processed fabric according to inventive process 83 85 1. 21 1. 25 28 28 Fabric treated only with solution B EXAMPLE 5 this way, a solution (referred tohereinafter as solution D containin l9 ercent of titanium trichloride was obtained. A

5 of conclammted hydioqhlonc acid and water treating li uor iw'as prepared, in a similar way as in the foregowere charged into a flask similar to that used in foregoing Exi n g Example 4 from 50 percent of Said solution D 12 percent ample 3. With the flask being water-cooled from outside, 19 g. 5 of nMykon (30 percent poxyethylene emulsion) and 38 of "'P tetrachloride were added to the ,liquid mixture percent of water. A similar half cardigan knitted from nylon 6' f further of Swnnous chloflde 12 of threads was dipped in the liquor in the similar way as disclosed metallic tin powder were added to. The reaction mixture was in the foregoing Example f for 2 hours adoded of ,mamum The material thus treated and conditioned as before showed f' h f"? kept at 30 reactfon' thls a 10 satisfactory dullness and linen-like touch, yet being conhcluld f f g Percent of l qf "Y siderably flexible, without appreciable loss of strength. tamed- T1115 llquld W be s e iees l qetdrcv h W f t- While a similar fabric treated only with solution D showed A half cardigan, coarses 63 and wales 28, front thread being equally favorable dullness and soft touch, it showed too much of nylon 6, d./ 12 fiL, rear thread being of nylon 6, 15d./lf1l., paper-like feelings to be used for clothing purpose. was dipped in a liquor prepared from 50 percent of said solul5 The physical properties of the fabric treated in accordance tion C, 10 percent of Mykon SF percent polyethylene ,with tl 1e novel process are enlisted in the following Table VI.

TABLE VI Transparency Soltness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries Non-treated fabric 100 101 90 86 18 18 Processed fab. according to inventive process 84 87 82 82 15 15 Fabric treated only with solution s2 s2 15 2s 11 12 emulsion) and 40 percent of water, squeezed to a 70 percent- 30 EXAMPLE 7 pickup, and then heat treated in the similar way as in the foregoing Example 4.

The thus conditioned fabric represented superior full-dullness and cotton-like touch, without inviting any appreciable paper-like feelings and without appreciable loss of strength. W feelmgs pecilhar to nylon 6 fibers Y Substamlauy ob- 2 percent of hydrochloric acid and 12 percent of Mykon SF" viated and the desirous dullness and the like favorable charac- (30 percent polyethylene emulsion) and squeezed to 30 tensucs i e dlsapgear S afterpemg subjected to as cent pickup. This wet fabric was heated at 100 C. for 3 memusas 19 95 FPPWUSPQ EBQPE minutes and showed full-dullness and enough strength for A half cardigan, coarses 63 and welts 28, either front or rear thread being of mixed filaments, nylon 6 and rayon, 50 d. 17 fils. and 50 d /20 fils., respectively, was dipped in a treating liquor containing 7 percent of chlorinated barium titanate, 3 percent of barium chloride, 10 percent of titanium trichloride,

- MmwTTP 40 Q P Q h a slmllar raw fabnc w'hlch was treated P y clothing purposes, while a similar fabric treated only with a with 581d I00 heavy P p feel was Obtamed titanium trichloride-containing solution represented substanfor use for clothing P TPQ 7 tially inferior strength.

In the following Table V, the results of the comparative tests The physical properties of the fabric treated in accordance are listed. 7 i. s u H with the novel process are listed in the following Table VII.

TABLE V Transparency Softness 1 Strength, kg.

After five After five After five Before times Before times Before times laundrics laundries laundries laundries laundries laundries Non-treated fabric 100 101 87 89 17 18 Processed fabric according to inventive process 71 73 80 82 15 16 Fabric treated only with solution C 4 69 10 21 9 10 1 softness given was measured by the slide process (see, Japanese Industrial Standards, 1079, 5-17) The results were of themean valu w of those of longitudinal and lateral directions.

TABLE VII Transparency Softness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries N on-treated fabric 100 102 94 15 14 Processed fab. according to 10 inventive process 85 88 83 87 10 7 Processed fab. only with T101 82 84 10 18 6 EXAMPLE 6 EXAMPLE 8 10 g. of concentrated hydrochloric acid, 20 g. of magnesium 70 A crepon fabric, 113 warps X 98 wefts, said warp being of chloride and cc of water were introduced into a flask nylon 6, 70 d./24 fils., and said weft being of polypropylene, similar to that employed in the foregoing Example 2. As in Ex- 70 d./24 fils., was dipped in a treating liquor containing 40 ample 4, 20 g. of titanium tetrachloride was added to dropwise percent of said solution C, 8 percent of Marpozol PO, and then 40 g. of titanium tn'chloride and 25 g. of magnesium manufactured by Matsumoto Yushi Seiyaku Co., Ltd., Osaka, foil were added to. The mixture was reacted at lQfT-AQZQ, I11 75 Japan, and 52 percent of water, squeezed to a 36 percent pickup, heated at 50 C. for 4 minutes, water-washed and dried up.

The thus processed fabric showed superior full-dullness and moderately soft touch vithout any appreciable loss of strength, while a similar fabric subjected only to said second treating stage represented too much paper-like feel and reduced strength to be used for clothing purposes.

The results are listed in the following Table X.

TABLE X Transparency Stiftncss Strength. kg.

After live After five After th-u Before llllllS Before tlnns lhloro tlntns laundrres lnnndrles lnnnttrius lnntulrics lnuntlrlcs lnnntlrlos Non-treated fabric 100 101 t. to 1. on 2n 30 Processed fabric according to inventive process 78 81 0. 7t) 0. 83 '26 26 Treated fab. in the absence of polyethylene emulsion 76 78 0. 23 0. 33 15 16 strength, while a similar fabric treated only with the solution C represented a considerably reduced strength and accentuated paper-like feel.

In the following Table VII], the results are shown for comparison.

" E'XAMPLEM A nylon o-taffeta was dipped in an aqueous dispersion containing 10 percent of titanium trichloride, 2 percent of calci- "I" eleeqeei s of et eiteqe e ee e. 1

A nylon 6-tafieta was dipped in an aqueous dispersion solution including 10 percent of titanium trichloride, 13 percent of zinc chloride, 3 percent of hydrochloric acid and 12 percent of Mykon SF, and squeezed to a 39 percent pickup. The wet fabric was then heated at 80 C. for 3 minutes, water-washed and dried up.

The resultant properties of the fabric were highly superior in its full-dullness and medium softness, without any appreciable loss of strength. A corresponding fabric treated similarly, yet in the absence of Mykon SF," showed a poor strength TABLE VIII Transparency Softness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries launclries Non-treated fabric 100 101 1. 1. 32 31 Processed-fab. according to inventive process 83 85 1. 21 1. 25 28 28 Fabric treated only with solution C 81 82 0.36 0.61 20 24 V n EXAMPLE 9 cent of hydrochloric acid and 12 percent of silicone oil emulsion (Silicolan 21, manufactured by lpposha Oil 1nd. Co. Ltd., Osaka, Japan), squeezed to a 36 percent pickup, heated at 1 10 C. for 3 minutes, water washed and dried.

The thus treated fabric showed considerable improvement in dullness and cotton-like touch, without considerable loss of strength, while a similar fabric subjected only to said second treating stage represented too much paper-like feel and sleseietsensth E9 Pe e f rde Revises; m t The results are shown in the following Table X1 in a comparative way. i

TABLE XI Transparency Softness Strength. kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries Non-treated fabric. 100 94 1. 10 1. 04 31 30 Processed fabric accor inventive process.. 77 79 0.83 0.88 28 28 Fabric treated similarly,

the absence of silicone oil emulsion 76 78 0. 31 0. 33 19 18 EXAMPLE 12 and a considerably reduced stiffness.

The results are shown in the following TABLE [X in a comparative way.

A nylon 6,6-taffeta, 1 l0 warps 101 wefts, both being TABLE 11:

Transparency Softness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries Non-treated fabric t 100 101 1. 10 1.09 30 29 Processed fabric according to inventive process 77 78 0.86 0.90 27 27 Fabric treated similarly, jet in the absence of Mykon SF.-.

m EXAMPLE 10 d./24 fils., was treated in the same way as in the foregoing Example 3. The results were similar to those obtained therein.

The results are shown in the following Table XII in a comparative way. 7

EXAMPLE is A half cardigan of nylon 6 was printed with use of a-mixture of a surfactant of oxyalkyl amide type (Dianol 330," manufactu refl by Daiichi Kogyo Seiyaku Kabushiki Kaisha, Japan) TABLE XII Transparency softness Strength, kg.

After five After five After five Before times Before times Before times laundries laundries laundries laundries laundries laundries Non-treated fabric 100 101 1. 04 0. 94 35 34 lroccssed fabric according to inventive prccss 78 78 0,80 0.84 28 '27 Fabric treated only with solution C 76 77 0.32 0.57 19 19 and 47 g. of printing paste comprising: EXAMPLE l8 much 2''; A twilled fabric, 72 warps X 55 wefts, nylon 6T, 35 d., was 8mm] sum 7% ;printed with a paste obtained from: the solution A (refer to water 72% Example 6) 35 percent, Mykon SF" (refer to Example 2) 15 EXAMPLE 14 A half cardigan composed of mixed yarns of nylon 6 and rayon was treated in the same way as disclosed in the foregoing Example 13.

The results were substantially the same as before.

EXAMPLE 15 In place of the half cardigan employed in the foregoing Example 16, a georgette, 150 warps X 126 wefts, warp being of nylon 6, 30 d./6 fils. and weft being of rayon, 40 d./ fils. was used and the treating conditions were substantially the same as those in the foregoing Example 16. The results were substantially same as in the Example 16.

EXAMPLE 16 A printing paste was prepared from 30 g. of the solution A (refer to Example 3) and 40 g. of a surfectant of polyethylene grycol alkyl ether type (Noigen HC, manufactured by Daiichi Kogyo Seiyaku Kabushiki Kaisha, Japan) and further 60 g. of the paste-forming material as referred to in the foregoing Example 13 and designs were printed on a nylon 6-taffeta with the thus prepared printing paste.

The results were substantially the same as in the foregoing Example 15.

When the printed fabric thus prepared was dipped in a dyeing bath containing 0.05 percent of a dye staff (Cibacet Brilliant Pink FG, manufactured by Ciba Ltd., Basel), taken out squeezed and heated at 100 C. for 60 minutes, as conventionally. The printed designs were slightly colored and non-:

transparent, but the remaining substrate areas are strongly dyed and somewhat transparent. Upon successive 10 or more launderings, the designs were subjected to practically no adverse effects.

EXAMPLE 17 A tafi'eta of N-methyl-nylon 6, 10, 113 warps X 99 wefts, of 70 d./24 fils., was treated substantially in the same way as in the foregoing Example 16. The thus printed designs were brilliantly white and soft in its nature and remarkably distinct from the remaining substrate area. Even after ten or more successive laundry tests, the designs were not substantially adversely afiected.

percent and a paste 50 percent, the latter being prepared from starch 20 percent, British gum 8 percent and water 72 percent. The printed fabric was heated at 120 C. for 5 minutes, washed wifiyvater and desize d. 7M p u The printed designs were brilliant white, penetrating through the fabric, soft in its nature and remarkably distinct from the remaining substrate area. Even after ten or more times successive laundry tests, the designs were not substantially adversely affected.

EXAMPLE 19 A nylon taffeta, dyed by a dye stuff solution containing 0.05% of Cibacet Violet 2R," manufactured by Ciba Limited, Basel, by treating at C. for 60 minutes was printed with a paste containing 30 g. of the solution B (refer to Example 4), 25 g. of Mykon SF, 15 g. of starch and 45 g. of water. The printing conditions were similar to those employed in the foregoing Example 18. In this way, a brilliantly white, non-transparent design appeared on the fabric having a thick violet color tone on the non-printed areas thereof. The printed white design was not adversely affected even upon successive 10 or more launderings.

EXAMPLE 20 A yellow printing paste was prepared from:

titanium trichloride 10% Mykon SF" (30%-polyethylene emulsion) 30% Water-dispcrsible yellow pigment Acramin Yellow F70." manufactured by Farben Fabriken Bayer A.G.,

Lcverkusen, Germany 1% starch 15% water 44% and printed on a nylon -taffeta. The printed fabric was dried at 70 C. for 3 minutes and then heated at for 3 minutes, followed by washing with water at 80 C. and drying. The yellow printed designs were highly brilliant, soft in its nature and remarkably distinct from the remaining substrate area. Even after 10 or more successive laundry tests, the designs were not substantially adversely affected.

EXAMPLE 21 titanium trichloride 10% Norane Silicone SS (BOEE-silicone resin emulsion), manufactured by Warwick Chemical Co., Rhode Island, U.S.A. 15% waler-dispersible pigment,

Fast Yellow A," manufactured by Farbenfabriken Bayer. Leverkusen-Bayerwerk. 2% starch 15% water 58% are processed as usually to prepare a printing paste which was then printed on a nylon 3-tricot, dried at 70 C. for 3 minutes and then steamed at 98 C. for 10 minutes. Then, the fabric was washed with warm water ((2 C J and dried "PP; The

resultant print was superior and its characteristics were substantially the same as in the case of Example 20.

The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

What we claim is:

g l. A method for processing a polyamide-containing fibrous material which comprises contacting said material with TiCl in an amount sufficient to swell the polyamide fibers, and with a separating agent adapted to separate the swollen polyamide fibers from each other in an amount sufficient to cause separation of the polyamide fibers from each other, carried out at a temperature of from 50 to 160 C. for a period of time of from 30 seconds to 10 minutes. v

2. The method of claim 1 wherein said contacting is carried out in two stages, said fibrous material is first contacted with said separating agent at a temperature of at least room temperature and is thereafter contacted with said TiCl at a temperature of from 10 to 150 C. for a period of time of from 1 to minutes.

3. The method of claim 1 wherein said fibrous material is contacted with said TiCl in a liquid phase.

4. The method of claim 3 wherein the contacting is performed in'the presence of at least one auxiliary swelling agent compatible with said TiCl and adapted to swell the polyamide fibers.

5. The method of claim 4 wherein at least one of said auxiliary swelling agents is a carboxylic acid selected from the group consisting of formic acid, monochloroacetic acid, cyanoacetic acid, monochloropropionic acid, malonic acid, acrylic acid, glyoxal acid and combinations thereof.

6. The method of claim 4 wherein at least one of said auxiliary swelling agents is a mineral acid selected from the group consisting of HG HBr, HNO H 80 oand p-phosphoric acid.

7. The method of claim 4 wherein at least one of said auxiliary swelling agents is a sulfonic acid selected from the group consisting of benzenesulfonic acid and toluenesulfonic acid.

8. The method of claim 4 wherein at least one of said auxiliary swelling agents is a metal halide.

9. The method of claim 4 wherein at least one of said auxiliary swelling agents is a metal sulfate.

10. The method of claim 1 wherein said separating agent is a polyolefin.

11. The method of claim 1 wherein said separating agent is polyfluorocarbon.

12. The method of claim 1 wherein said separating agent is a silicone resin.

13. The method of claim 1 wherein said separating agent is a higher monohydric or polyhydric alcohol.

14. The method of claim 1 wherein said separating agent is a polyoxyethylene compound.

15. A method for processing a polyamide containing fibrous material which comprises contacting said material with an aqueous dispersion comprising:

at least 5 percent by weight of TiCl from 2 to 35 percent by weight of at least one auxiliary swelling agent, compatible with said TiCl and adapted to swell the polyamide fibers,

and from 2 to 45 percent by weight of a separating agent adapted to separate the swollen polyamide fibers from each other, for a period of time of from about 30 seconds to about 10 minutes at a temperature of between-50 and 160 C.

16. A method for processing a polyamide-containing fibrous material which comprises contacting said material with a printing paste comprising:

from 2 to 45 percent by weight of TiCl from 0.5 to 15 percent by weight of a suitable separating agent adapted to separate the swollen polyamide fibers from each other,

and from 2 to 25 percent by weight of a starch, for a period of time sufficient to swell and separate the polyamide fibers.

17. The method of claim 1 wherein said TiCl comprises a mixture containing from 1 to 18 percent by weight of Ticl said mixture being the reaction product of TiCl, with a metal selected from the group consisting of zinc, iron, aluminum, magnesium, calcium, and barium, or halides thereof, in the presence of an acid.

18. The method of claim 1 wherein after said contacting, said polyamide-containing fibrous material is cleaned with water to remove any remaining TiCl and separating agent from said polyamide-containing fibrous material.

19. The method of claim 3 wherein said liquid is water or an organic solvent.

20. The method of claim 15 wherein said TiCl comprises a mixture containing from 1 to 18 percent by weight of TiCl said mixture being the reaction product of TiCl, with a metal selected from the group consisting of zinc, iron, aluminum, magnesium, calcium and barium, or halides thereof, in the presence of an acid.

31. The method of claim 20 wherein after said contacting, said polyamide-containing fibrous material is cleaned with water to remove any residual TiCl;,, auxiliary swelling agent and separating agent from said polyamide-containing fibrous material.

22. The method of claim 16 wherein said contacting is conducted for a period of time of from about 1 to about 8 minutes at a temperature of from about 50 to about C.

* i l I 

2. The method of claim 1 wherein said contacting is carried out in two stages, said fibrous material is first contacted with said separating agent at a temperature of at least room temperature and is thereafter contacted with said TiCl3 at a temperature of from 10* to 150* C. for a period of time of from 1 to 5 minutes.
 3. The method of claim 1 wherein said fibrous material is contacted with said TiCl3 in a liquid phase.
 4. The method of claim 3 wherein the contacting is performed in the presence of at least one auxiliary swelling agent compatible with said TiCl3 and adapted to swell the polyamide fibers.
 5. The method of claim 4 wherein at least one of said auxiliary swelling agents is a carboxylic acid selected from the group consisting of formic acid, monochloroacetic acid, cyanoacetic acid, monochloropropionic acid, malonic acid, acrylic acid, glyoxal acid and combinations thereof.
 6. The method of claim 4 wherein at least one of said auxiliary swelling agents is a mineral acid selected from the group consisting of HCl HBr, HNO3, H2SO4, o- and p-phosphoric acid.
 7. The method of claim 4 wherein at least one of said auxiliary swelling agents is a sulfonic acid selected from the group consisting of benzenesulfonic acid and toluenesulfonic acid.
 8. The method of claim 4 wherein at least one of said auxiliary swelling agents is a metal halide.
 9. The method of claim 4 wherein at least one of said auxiliary swelling agents is a metal sulfate.
 10. The method of claim 1 wherein said separating agent is a polyolefin.
 11. The method of claim 1 wherein said separating agent is polyfluorocarbon.
 12. The method of claim 1 wherein said separating agent is a silicone resin.
 13. The method of claim 1 wherein said separating agent is a higher monohydric or polyhydric alcohol.
 14. The method of claim 1 wherein said separating agent is a polyoxyethylene compound.
 15. A method for processing a polyamide containing fibrous material which comprises contacting said material with an aqueous dispersion comprising: at least 5 percent by weight of TiCl3, from 2 to 35 percent by weight of at least one auxiliary swelling agent, compatible with said TiCl3 and adapted to swell the polyamide fibers, and from 2 to 45 percent by weight of a separating agent adapted to separate the swollen polyamide fibers from each other, for a period of time of from about 30 seconds to about 10 minutes at a temperature of between 50* and 160* C.
 16. A method for processing a polyamide-containing fibrous material which comprises contacting said material with a printing paste comprising: from 2 to 45 percent by weight of TiCl3, from 0.5 to 15 percent by weight of a suitable separating agent adapted to separate the swollen polyamide fibers from each other, and from 2 to 25 percent by weight of a starch, for a period of time sufficient to swell and separate the polyamide fibers.
 17. The method of claim 1 wherein said TiCl3 comprises a mixture containing from 1 to 18 percent by weight of TiCl3, said mixture being the reaction product of TiCl4 with a metal selected from the group consisting of zinc, iron, aluminum, magnesium, calcium, and barium, or halides thereof, in the presence of an acid.
 18. The method of claim 1 wherein after said contacting, said polyamide-containing fibrous material is cleaned with water to remove any remaining TiCl3 and separating agent from said polyamide-containing fibrous material.
 19. The method of claim 3 wherein said liquid is water or an organic solvent.
 20. The method of claim 15 wherein said TiCl3 comprises a mixture containing from 1 to 18 percent by weight of TiCl3, said mixture being the reaction product of TiCl4 with a metal selected from the group consisting of zinc, iron, aluminum, magnesium, calcium and barium, or halides thereof, in the presence of an acid.
 22. The method of claim 16 wherein said contacting is conducted for a period of time of from about 1 to about 8 minutes at a temperature of from about 50* to about 100* C.
 31. The method of claim 20 wherein after said contacting, said polyamide-containing fibrous material is cleaned with water to remove any residual TiCl3, auxiliary swelling agent and separating agent from said polyamide-containing fibrous material. 